Treatment of calcium sulfite



Nov.'2,1948. H R, RAFTON `2,453,099

TREATMENT 9F CALCIUM SULFITE Filed Oct. 4, '1943 I [will] l 5 f HQPOLDRPAFTo/v l f n y HWI Patented Nov. 2, 1948 UNITED STAT Es PATE NT OFFICE y A, TREATMENT OF CALCIUM SULFITE Harold R, Ratten,` Andover, Mass., assigner to eration, a corporation of Raiold VProcess Corp Massachusetts Application october 4, 1943, seriaiNQ, 504,921

l o1. ,z3- 129) 14 Claims.

' Myuinventio'n ,relates to the treatment of cal- 'cium sulphite.`

` `"The `principal object `oirny invention is the treatment of calcium sulphite` to'impart specic 4and controlled improved characteristics thereto.

Aiurther object is the production-of improved i filled paper and coated `paperwith said treated `calcium sulphite.

treatment of slaked limev or calcium carbonate with sulphur dioxide; by `the precipitation ofa soluble calcium `salt suchlas calcium chloride with `asoluble sulphite such as sodium `sulphite; by theprecipitation of a solution of calcium bisulphite as byreduction in pressure, or by boiling, or by addition oian alkali such as sodium, hydroxide or slaked lime thereto; by the treatment of a mixture of cal=cium-chloride and magnesia with sulphur dioxide; and the likeythe `formation of the calciurnsulphite usually `taking placein the presenceof a greater or lesser amount ofwater.V C l i i l i Inrecentyearsicalcium sulphite has come into commercial use as a `iiller for paper and as a coating pigment for paper.` `While it produces paperswhich have in generalbeen acceptable to the trade, nevertheless certain properties of calcium sulphite are not i all that could be desired vto produce paper of the best quality. For eX- 4ample in -coatedxpaper,lthe `calcium sulphite has a relatively hignadhesive requirement-and a relatively high oilabsorption; and moreover imparts afnishwvhich is not as glossy as Adesired in many cases. In filled paper rmadetherewith, the inkiabsorptivequalitiesare sometimes too high7 theiinish is sometimes irregular or not 'sufiiciently glossy,and the l:feel not always as smooth asdesired 4 l I. HI, have devisedfa `process .iorttreating calcium s ulphite which overcomes to ailarge` extent,` if i indeed it Adoes not `completely eliminatethe undesirable properties possessed by calcium sulphite and imparted `it to the paper `rnade therewith. My process accomplishes thisi without any substantial detriment to the otherwise satisfactory `properties of` the calcium sulphite, such as whiteness, brightness andthe like.` lin-fact iteven enhancesthese properties,:particularly in coated paper, because of thelesseradhesive requirement aswell aslthe greater ease of finishing.- l

I hav`edescribedin detail in my above iieez nieu`Ju1yf2]1942,`and 543,469 med August 3, "1942, now abandoned in favor, respectively, `oi

my continuinglappllication SerialNo. 718,649, led

December27l946, `nowPatent No. 2,447,532, is-

suedAugust 24,1948, land my continuation inpart application Serial 740,831, iiled April 11,

1947, now` Patent No. 2,451,448, issued Qctober l2, 19,48, I have `(.lisclosedthat bystriking a pigment comprising calcium carbonate in"` association with .water, in liquid form or inpaste form respectively, with a striking Surface of a rotating, e. rotor,- elementhaving a velocity of not less `than substantially 3x0 feet per second, I am able `to impart to saidpgigment, characteristics hitherto impossible of acquirement, or, iihithel` to possible of acquirement by differentmethods,

onlyat considerable` expense orto `a relatively minor degree; andi have` producedpigment with modified and in some cases unique characteristics.

`Ihave also found that by the application of. the

treatment` to `calcium sulphite Iam able similarly rgreatly" irriproved` paper therewith.

mentioned copending applications" the `equipment which I- employ for carrying out `my treatment and thedisclosure of said applications is hereby made a parthereof for thepurpose of crossreference. Briefly, my method comprises the subjecting of calcium sulphite in associationwith water inthe form of a liquid .or in the form `oi a paste,

totheaction of a, striking surface of a moving element. Ap-preciable results are obtained when employing a velocity `of not less than substantially 30 feet per second, `but. better results` areob- ,tained `when employing higher velocities, usually not less than 100 feetper second and preferably at least 200 feet `per second, or evenbetter of S00 feet--5004ieet lor more per `second` `liind yitmost `convenient `to use a rotating element equipped with striking; usuriaceor. surfaces, prefcrab-ly a rotating ele-ment rotating at high speed.

It is feasible; tocarry out` my invention bythe i use of any one of `a large variety ofgipieces of l equipment, for example,` bythe `use, ofearotating striking surfaces may ,bei arranged on 'the` periph-` ery ofrthe rotating element, for example a disc 3 similar to the arrangement of a steam turbine wheel, or juts, blades, teeth or other striking surfaces may be arranged on the end face or faces of the disc rather than on its periphery. The striking surfaces employed. need not be an integral part of or rigidly attached to the rotating element, butmaynbe attachedas by fpins, hinges or'the like; and if desired,'in certainfcases, may swing out for example by centrifugal force.

The disc referred to may be vertically disposedl with its drive shaft in a horizontal pl'ane or may be horizont-ally disposed with its drive shaftin a vertical plane or at any other angle desired.

Because of the convenience. of operation and the simplicity of the bearings required for the drive shaft of the disc, I prefer, however, to employ a disc disposed vertically, that is, withy the shaftin.Av

a horizontal plane.

Although as stated, avariety of pieces of equipment will fulll the requirements of my process, from the standpoint of economy and convenience, I prefer to use either a circular ysaw ora` hammer mill. 4Of course the hammers of the hammer mill may be attached to more than onedisc'or the like, usually to two' or. more spaced on the drive shaft.' Theliquid or paste comprising the calcium sulphitelrn'ay be subjectedv to the striking surfaces 'of the rotating element inV bulk form if desired; or in jet or shaped'form', either in a direction substantially opposed'to that of the .direction of advance of the leading .faces of the striking surfaces', or otherwise, but preferably in a direction parallel to the leading faces', preferably in a plane of rotation of therotating element from beyond .the periphery thereof and directed toward its center of rotation. The leading v'faces of the strikingsurface or surfacesare preferably arranged radially in respect`to the rotating element or come 'into that position when in operation; Whenusing a liquid, 'I prefer to employ the type'o-f machine' described in my copending application SerialA No..479,373, led March 16, 1943, now Patent No. 2,448,049, issued August 3l, 1948,'1'. e., the soecalled Rafton mill and'v when using a paste I prefer to'use a hammer milL'preferably f ed from a feeding point or points in the periphery of thecasing thereof, although such'a feeding point or points is notessential. However', if desiredfthe hammer mill may be employed when using a liquid and the Rafton mill when using a paste. I may subject the calcium sulphite to only one passage throughthe apparatus employed, but usually improved resuits can' be obtained by more than one passage or pass and thus I prefer to pass thecalcium sulphite through the apparatus more than once, usually employing from live to twenty passes or more.

As indicated above, the preferred machines for carrying out my process' are either a Rafton mill or a hammer mill. As the Rafton `mill is describedin greatdetail' with adequate drawings in my copending'applicat'ion' last above referred to, itis not necessary to "include a drawing there- 'of herewith, but a drawing of a'hammer mill the hammers and discharged through an opening in the mill casing. In this showing:

Figure 1 is a sectional view of a hammer mill, parts being shown in elevation,

Figure 2 is an enlarged sectional view, 4in fragmentary form, of that portion of Figure 1 adjacent .the juncture of the...inlet. conduit., and the hammer .mill casing, and,

Figure 3 is an enlarged sectional view, in fragmentary form, on line 3-3 of Figure 1.

Referring to Figure 1, casing I0 is provided witl'rin'let` conduit II and outlet I2. Inlet con- .duit II is fed by appropriate means such as inlet I3, shown in fragmentary form, connected thereto at its free end, and snugly houses screw conveyor I4 mounted on shaft I5, driveable in the direction'of the surrounding arrow by any suitab-lemeans (not shown) and communicating through casing I0 by means of substantially circularaperture. I5 therein. ,Throughthe casing I0 extends shaft I'I on which is mounted plate I8, which rotatable. in.l eitherdirection as, desired,fbut.is..here shown as rotatingin, a,.clock wise. direction.. .(PlatelIS, is one lof twosimilar plates, spacedlymounted :on shaft. I'I., the .second of' which: is shown, only .in Eigure.) ...In holes I9 in plate I8, hammers 20 are swueled on their respective= pins-21 each. of vwhich maybe integral with its associated hammer 20- In operation, as exempliedin Figurel,4 shaft I1 is driVen-athigh speed.r whereby .plate 4HI,` securely lxedltheretd, is rotated,tthereby in turn rotating -at high .speed -hammersf 20? which swing out by centrifugal force. substantially along radial lines of plate I8. Paste^22 isintroduced into in.- letv I3', advanced in inlet conduit I I1 by meansr-.of screw `conveyor I4, and eXtrudedthrough-aperture Isubstanti-ally as a continuous massi ofcircularcross-section.. Successive smal-1 portions or slices of this mass of. paste .22i are struckfoff by rapidly rotatingfham-mersz 20, andare discharged through outlet I2 as discharged; material' 23 (shown, .diagrammaitically);,if For. greater :efficiencypaperturefl may :be lreducedfin, sizemto the form of a horizontal slot, thereby presenting a ribbon of'f paste Yinsteadoi" aimass of circular cross-'sectiontto the action of hammers :20. 1 'If a slurry is used'as feed; screw conveyor I4 may still be employed, but it is not necessary and may be dispensed'with and'the'lslurry fed directly into inlet` I3; or, if desired, inlet I3, inlet conduit' II and screw conveyor I4, may all be dispensed with andthe slurry K.fed intothe path:of the hammers e. g; under pressure as a jet, such as by a nozzle (not shown) .tightlyafXed-in aperture I6.

Referring to Figurez, the vertical dotted lines I shown at the end ofthe extruded portion of'the paste illustrate, diagrammatically,` rsuccessive small-portions or slicesof: pastel struck off by the blow of successive hammers 20 asthey'pass in front of the aperture I6. It will be understood that the-'thickness of `each 4successive vportion struck off will depend upon'thefrelative'peripheral speed of the hammersg' and ofthe advancing mass of' extruded paste.2'2."` If such mass of paste 22 advances relativelyv slowly with respect to the peripheral speed of the hammers 20, asis usually the case, the portionsv will be relatively thin, but if the paste advances relativelysomewhat more quickly, the portions will be somewhat' thicker.

In Figure 3,the dotted line shows the advancing edge Vof one ofthe hammers'Z at the point of striking the'upper side of the paste 22 being extruded; Dischargedmaterial' from the prelas beingdischarged through' outlet I2.

,Inmy -copending application Serial No. 455,367, ri'lled August 19, `1942,the disclosure of whichis madea parthereofiorpurpose of cross refer ence, I h-ave disclosed that by striking a pigment comprising calcium carbonate in association `with, sufficient `.waterto form a crumbly mass, with a striking surface of a rotating element havfeetper second, I am -able to impart to saidpigment characteristics similar to those imparted by the processes of my two other` copending applications `ilrst mentioned herein. I have also -found that by the application of the treatment `l of 'applicationf Serial `No. @455,367 to calcium sulphite, I am able to modify said calcium sulphite similarly to the modification obtained when said calciumsulphite is treated in liquid or paste form.

reduce theadhesive requirement from 1U `to 70% `or more, I can reducevthe oil absorption from `10 to 50% or more,lI canincrease the, gloss `imparted to coated paperfrom 10 to 50% or more, and the like; and where in thelclaims Irspeakof effecting a change in at least onetof` the properties ,of adhesive, requirement, oil absorption and glossing a velocityv of not less than substantially,30H10,`

imparting qualities. of said calcium sulphite of hesive requirement or oil absorption that the `change results in areduction of `not less than :one-tenth of theoriginalwvalue of .said respective property, and in the case of glosseimparting ,qualitythat the Change results inan increase of not less than one-tenth of the original value of, said property. w l

Cross reference is' likewisemade tomy copend-` 20 I shallnow illustrate the preferredprocedures `ing 'application ,SerialNo 584,158, filed March 22, `for practicingmyinvention. 19,45, `also relating to the treatment of` calcium I give the following example as `illustrativeof carbonate. Applications Serial Nos. 455,367 the results obtained in carrying out my process and 584,158 have now been abandoned in favor `when calcium sulphite is used in association with of my application Serial No.` 706,907, led October water in the form cfa. thick liquid `01V slurry- 31, 1946, as a continuation in partof my said two Calcium sulphite made by action of sulphur diprior applications. The amount of waterreoxide on aslurryof slakedlime '(the" commonest quired to produce a crumbly mass with calcium `commercial methodof` making calcium sulphite), sulphite, varies with the particle size and other was subjected; to treatment in, a Rafton mill. characteristics of the material, but usually when The calcium sulphite employed had an original the resultant material contains from about 10% dry Content Wlell the T1l1'lWeS Started 0f, 362%, to about 20% `o1 water, it exists in such condition, but it thickened, Slightly due te ,l'leerpe'eten 0f y that is, in a .condition in which the material is air as therun proceeded,-`so thata little water in crumbly form', but does not form a coherent was added during the run, and the nal dry whole. It will be understood that the ouby'g5 "content'was 29.75%. The addition of a little pine condition `existsthroughout, arange of Water conoil ,or other similar. agentis usefulin` combatting tent whichvvaries-with conditions.` ,With the adthis incorporation of air, `but `none was used in dition ofv further water, the material is converted ,this llln- The jet Speed 0f the .Sllllry treated in `to a Coherent, plastic condition or paste. `I the run was about,` 86.` per sec., the pressure ,of` maycarry out, my invention with calcium lo the Dump Supplying `'011e slurry 'being SJPDIFOXF sulphite where enough Water is present `merely metely 70 lbs! pelsquefe inch-i The Velocity toformla` crumbly solid, using for the purpose the 0f the periphery 0f the rotating elementi temi" equipment `previously described, and conveniently DlOyed; inl/his Cese `vile Oli-tel :ends Of` the teeth a hammer mill. However, when thus treated, Of elv CICuaISeW. ,Wes 478'l0er`SeC011d- Thellln the material usually dries out rather rapidly Was continued for` 20 passes, Samples being Withduring treatment and thus requires the incordrawn atthe intermediate passes and. tested. poration of further water to keep it in the crumbly The` casein lreqllremenl." and` .oil absorption. condition, my process not being eiTective for were both `determined. by the methods customary modifying calcium ,sulphitewhen fed to a hamin the art, referredto in detail in `mycopending mer min in a dry powdery condition in bulk form. .zo application Serial No- 4419,492 now abandoned. The calciumsulphite, `in crumbly form is thus The percentglosslof the coatedpaper was demore diliicult to handle, especially when multiple .termined bydthe Ingersoll Iglarimeter on paper passes are employed as is customarily the case. coated withthe pigment, after the coated ipaper Thus the treatment of calcium` sulphite with only had been caIendered. l The results are tabulated sufficientwater to convert it into the crumbly .35 vin Table I. f l

Table I i Per cent rc f Y j RCasein, lggngl" "O ldb Percent Noofpasses, rncgililtef. ,q-lglt". sorlption (ilcliribssr. glzsahb per cent Original as i onorig. as paperI n 11cm-j owrigjsamplamb.. 56:2 E"inf-5 sov 41.7 17 w42 s.-. `1r` l 33.7. s3 l, 44.5 14 l 32.2 se l42 1s i 29.1` 42 5s is ,3i-.s s?, to

form is my non-preferred procedure,` mypre-` ferred procedures beingthe treatment of said calcium sulphite either in a `liquid or, paste condition. lI n the practice of my invention, I; am able to 75.111 gloss@ 3. s

, ,Aniexamination of the data :ofTable I shows that treatment by mypprocessfhas resulted inca very great ,reduction `incaseinrequirement and oil absorption, asfwell as a, marked improvement I lgive the following example as illustrativefof the results obtained in oarryinglout. my process when calcium sulphiterisy used in association'with Water'in the form of a paste.` The calcium sul- Modified starch, which f is particularly effective for this purpose with calcium-iV carbonate,` does not seem'to` be effective with calcium sulphite C'asein solution, also effective with calcium-caru the eiciency of the treatment in liquid form by vtheuse of a thinning agent, which has been rephite in lpaste form, which acts to liquefy it. 'F

phite was made by the same method as the sample f5 bonate, is moderately'eifectivefwith calcium sul-- used in they preceding run. It was subjected phite. Tetrasodium-pyrophosphateand sodium to Ytreatment in a hammer mill. 'The calcium silicate, effective withclay, are not'veryeiective sulphlte employed had an `original dry. content with calcium sulphite. The. best thinning agent when the run was. startedof 45.8%, but owing I have so far found is ypolymerized sodium salts to evaporation the paste became somewhat. more `'10 of alkyl naphthalene sulph-onic acids (alkyl long con-centrated as therun progressed, the nal dry chain) known by the trade name of Daxad No. content being 61.6%. vThe paste wasted into l1. 1 or 2% or somewhat more of thispusually the path of the hammers through an opening in about'2%,. is very effective in liquefyin'g a caltheiperipheral casing of the mill by a screw concium sulphite paste, so that even at arelatively veyor arranged radially.. The velocity of the i515 high dry concentration a calcium sulphite paste periphery of the rotating element. employed, in may be reduced to liquid form-and-thus readily thiscase the outer ends of the hammers, was processed in a: Rafton mill vwith asubstantially 3494 per sec. The run was continued for 10 higher efficiency as to number of passes and passes, samples being Withdrawn at the intertotal power consumption'than in the case of the` mediate passes and tested; The various tests f2() run recorded in Table I. Thinning agents may were made as previously described. The results also be usedto soften la stiff p'aste of relatively thereof are tabulated in Table 1I. high .dry content `to make `it easierto handle;

Table II Per c-ent te' Percent re Casein (ggonnrr 0 1 b d ilictligonin 1Per cnri No' of passes Rrenlrlilte qnlllt sorlpion (tilor bszsrl gocsosaexti e percent orig'as onii; as paper 10o a gefe- Sample) gg ggf, gg 13 7o 29.1 46 49 13 70 27.6 49 54 An examination of the data' of Table II, as of Calcium `sulp'hte as ordinarily manufactured that of Table I, shows that treatment by my commercially does not produce a product 100% process has resulted in a very great reduction pure, but usually one analyzing from about 80% in casein requirement land oil absorption, as well to about 95%` or more calcium sulphite accordi as a'vmarked improvement in gloss. 40 ing to the raw materials employed and the con- A comparison of Tables I and II indicates that ditions of manufacture. The composition at Y results of approximately comparable magnithe time. of use depends also upon the'care taken tudes are yobtained when calcium sulphite is to prevent oxidation'subsequent to manufacture'. processed either in liquid or paste form. HOW- 4 However, my treatment is'efective to modify the ever, it takes more passes to achieve the results properties of calcium sulphite.: Whether'it be in the liquid form, at least in the examples illuschemically pure or of the ipurity of the usual trated above. This latter -is doubtless due to the commercially manufactured grades, or indeed if fact-that the calcium sulphite was present in a it be mixed with other material so that it vis lower concentration in the liquid form than it ,o present in percentages less than 80% in a pigwas in the paste form, `and the effectiveness of ment composition. the treatment increases rapidly with increasing The calcium sulphite vtreated by my process concentration. However, the eli'iciency of a may be utilized in coating mixes inthe manner Raftonmill (used in the run of Table I) in recustomary in the art, as the'only pigment, or in spect to power consumption is usually better connection with other'coating pigment or pigthan that of a hammer mill (used in the run of 'M mentsywith thep-roper'amount of adhesive, and Table II), and thus the treatment in liquid form any other ingredients desired to be employed, and is not at the disadvantage `which would be indapplied to either one or both sides of a paper r cated by the greater number of passes required. webeither on an ordinary coating machine, or Moreover, it is much easier to handle a liquid than on the paper machine itself by any of the devices a paste, and in many cases the over-al1 eicncy 60 used for the purpose. The coated paper so prois found tobe greater. when treatment is carried duced, in comparison with coated paper similarly outkin liquid form. Thus the choice between produced from a, gunnen-*grade of Calcium sultreatingin liquid or in paste form may Well be phite, but untreated by my process, may be made determined by the condition in. which :the calcium...6) with .a lesser percentage of adhesive, is less absulphite originally exists, or in whichv it is dev sorbent of oil base inks, has a better iinish, is 'Sil'ed t0 DIOdlllCe it fOI use, rather than 0n any whter and brighter owing to the lesser adhesive .preponderant economic advantage to be gained required (particularly if the adhesive be one by treating in one or the other form. which has a tendency to lower the brightness t is, however, possible to improve considerably 70 and whiteness of the paper with increase in percentage used), and in general is of greatly proved qualityl and characteristics. .I

In the manufacture of filled paper, .calcium suljv phitetreated by my process maybe incorporated in the paper mix, with or without otherpigments, in conjunction with any of the types of pulps ordiflariiy empiyed, together i with other ingredients l such as alum, size, starch, antioxidant' or oxidation suppressing ingredient, and thelike,` in accordance with the type of paper to bemade, and

i-stics of the lled paper as thoroughly as those of `the coated paper, the indicationsare that the lledpaper so pr-oduced in which thecalcium sulphite may `be, present anywhere from a few per-i.`

-ceritiup to 39% or more if desired, is -superior from the'standpoint of feel, from the standpoint of finish, particularly insupercalendered paper, and

also is less absorbent in .certaincasesof oil base` printing inks. Inl-general, it is superior to similar lled paper similarly produced with calcium sulphitefwhich has not been treated by my process. This' applies not onlyto ordinarylled paper but tolledpaper which may .be surface or tub sized ontliepaper machinef i AIn the illustrative runs in Tables I and II, I

have shown a reduction in casein requirementl of calcium `sulphite treated `by my process. This is the adhesive mostwidely used 'in coated paper. Similar percentage reduction in adhesive requirement of` calcium sulphite tre-ated by my `process maybe ob-tained with other adhesives employed inthe coating industry, such as starch,either unmodiedor more usually in modified form, glue, gums, or protein, proteinaceous, protein-like or protein-containing i adhesive derived from other sourceslsuchas soy-a bean, corn (zein) or the like,

casein (derived from milk) either in modified,

cor'nbined or soluble 'l-form, as well as other materials" useful fas adhesives in coated paper.

use, and then used dry, or 'after addition of water as desired.

Myfprocessis applicable to calcium sulphite of anyp'article size, from coarse down to the Very finest,A including `that in colloidal condition.` In

the'coarser particle sizes, there is usually some reduction in particle size broughttabout by my treatment, but inthe nner particle sizes, my treatment' h'asf little or `no effect on thetparticle size of the calcium sulphite which is subjected thereto. Regardless of particle size, however, and `of method of manufacture of 'the calcium sulphite treated, the modification effected in the properties thereof by my process is similar.

My process is not only applicable to calcium sulphite in the liquid, paste, or crumbly condition in the wet formin which it is produced, orloy` removing some water #therefrom but Without `drying the pigment, but it is also applicable to Calcium sulphite `which has been prepared in `wet formancllthen dried, that is to say, 'the dried pigment maybe wetfup to form a liquid, paste or crumbly mass and then treated in my process.

I know, calcium sulphite has neverbeen treated As explained in detail in connection with my i Vcopending applications Serial Nos. 449,492, 453,469

andf455,367, my treatment may be conducted as i a `batch'process or as a continuous process. Reference is'made to those applicati-ons for information as `to appropriate equipment in which either the batch or the continuous operation maybe desirablain certain cases at least, to provide for cooling devices, preferably water jackets and the l like. -Of course, if for any reason it be desired,

additional heat may be supplied. Also water may 1f .be added to compensate for evaporation. More-* over, if desired, `apmopriate means may be taken toflimit .the exposure of the calcium sulphite to air or other oxidizing agent, to eliminate or at least substantially reduce any tendency to oxidal tion which may exist.` Alsoif desired my process i may be carried out atisuperatmospheric orisub` c atmospheric pressure, instead of at substantially atmospheric pressure, which is preferred."`

Where I use in my process a liquid or paste` i comprising water and calcium sulphite, this liquid 2O, agent, other pigment or the like; and if the tal-` cium sulphite is to be used as pigment for coating paper, any other ingredient used in a coating mix may be employed. Moreover a coating mixl as` such containing the desired amount of adhesive may be employed, but lalthough thisjis satisfactory in some cases, usually it is not-as eflicient, because the concentration of the` calcium sulphite is gen-` erally smaller in such mixes than the concentra-` :tions at which it may be more efficiently treated.` Where I use in ,myprocess calcium` sulphite con-` taining sufficient water to convertit to a crumbly or paste may include 'a ,thinningzagena -antifoam solid, `I may have other material present therewith, if desired, pr-ovidingthe physical condition of the pigment is not substantiallyaltered thereby.;

I have not as yet determined the cause or causes, of theoutstanding modification of :the properties` of cal-ciumisulphite brought about by` its` subjection `to my process, but my` theory is that it is due to some changewhich takes place inthe surface characteristics of theindividual particles. It may be -that -the` physica1,- ,chemicaLi-electrical `or iother condition "oflthe calcium sulphite particles has i, been altered. `While incertain cases as indicated `above there may be some reduction inparticle size,

in other cases thereislnonaor substantially none,

and `my process is in noI `sense, .a grinding process vf per se, and if` any comminution in particlewsize occurs, it is purely incidental and does not account for the modification in properties brought about in"my process. indeed, as to" adhesivereq-uirement and oilabsorption, any decrease in particle size of a pigment is ordinarily accompanied by an increasein` those properties, "rather thana `decrease.

Itis, of course, well known to treatmaterials `inhammer mms lor the iik@ tc wmrmnute` them i or break down aggregates therein, but as stated, this is not the process'which I` employ. Further?A moresuch comminution operations for the most in the prior art in a` hammer mill to change its properties, such as adhesive requirement and the like, nor has calcium sulphite in association with Water been treated therein with the results disclosed herein. So farlas I know, no one has ever observed that any such i modification fol?` properties could take place in treating calcium sulphite in the mannerI treat it, prior toinyly invention thereof.

may be put, for example in cold Water paints, or in other paints, -enamels or coatings, or as a ller in rubber, rubber-like materials, plastics, putties or other articles of manufacture.l

It is to be understood that my invention is not limited in any Way by any theory expressed herein, or by its validity or invalidity, because regardless of` any theory, the results are as stated hereii.

f While I have described ink detail the lpreferred embodiments of my invention, it is to be understood. that the details of procedure, the proportion of ingredients, the arrangement v,of steps, and-the -mechanicaldevices used, are presented for purposes of illustration only, and may be Widelyvaried withoutdeparting from the spirit of my invention or thescope of the subjoined claims.

Iclaim:

1. In-the treatment of calcium sulphite, the method oi' modifying said calcium sulphite to eiect an improvement in atleast one ofthe properties of adhesive requirement, oil'absorption and gloss-imparting quality of said calcium sulphite, which comprises directing said calcium sulphite in--association with water into the path of Vtravel of 4a percussive member of a rotor element, subjectingfsaid calcium sulphite to a percussionffr-om said `percussive member, said percussivemember having a Velocity of not less than SO--eetper second at the'point of said percussion, said rotor element at the time of subjecting said calcium sulphite to the action o-f said percussive member being free from contact with said calcium sulphite'except in respect to said percussive member, said calcium sulphite `being free for movement upon, and at the point of, said percussion, said calcium sulphite being .propelled by said percussive member away ,from and out of the path of traveler said percussive member.

2. A process according to claim-1 in which said percussivemember 'has a velocity of not less than 100'f`eet per second at the'point of-said percussion.

3. A process according to claiml 1 in which said Apercussive'm'ember has a vvelocity of not less than'ZOOf'feet per second at the point of said percussion.

4. A process according to claim 1 in which said percussive member has a velocity of not less than 400 feet per second at the point ofsaid percussion. y

5. .A process according to claim 1 in which said calcium sulphite in association With Water is in crumbly; form.

.6. A processaccording to claim 1 in which said vcalcium sulphite in l association withv 'water is in the form of `a paste.

:7.1 A process according to claim 1 inwhich said calcium sulphite in association with water vis in the form of a slurry. i

8. A-.rprocessaccording to claim` 1 in which said calcium sulphite irl-.association with water .is in thefform of aslurryjand in which Said slurry contains a thinning agent. v

.r9.lsThe; method of modifying calciumsulphite which :comprises directing said calcium sulphite inassociationwith water, the form of Va paste, intoithe path of travel -of hammers ofca Yrotor element, subjecting said paste to.V percussions Troma-said hammers, said `.hammers :having a velocity of not less thanplOOy feet per vsecond at thempoints o'fxsai'd percussions, :saidrotor element attire-.time :ci subjectingsai-d xpaste tothe action ofsaidhammers bengfree from contactk with saidpaste'except in respect A.to said hammers,

said paste beingfree for -movement upon,lan,d

at the points of, said percussions, said-paste being.. propelled bysaid hammers away from andoutof the path of travel or said hammers, redirecting the thus treatedpaste into thepath of travel of said hammers, `and resubjecting it to the action of said hammers `a sufficient number of times to effect achange in at least one ofthe lproperties of adhesive requirement, oil absorption andgloss-imparting quality of said calcium sulphite of not lessithan one-tenth of the orig- Vv inal `value of said property. y

10; Ther-method of modifying calcium sulphite whichxcomprises directing said calcium sulphite in associationwith water into the path of travel of teeth of a -circular A`saw, subjecting said calcium sulphite to percussions -from said teeth, said teeth lhaving a velocity of not less than 1100 feet per sec 'ond -atfthe points of said percussions, said circularsa-W at the time of subjecting saidlcalcium sulphite to the action of said-teeth being :free` from contact with said calcium sulphite exceptl in respect to said teeth, said calcium` sulphite being free for movement upon, and at the points of, saidy percussions, said calcium sulphite being propelled by said teeth away from and out of the path of travel of said teeth, re-directing the thus treated -calcium sulphite into the path of travel `of said teeth, and resubjecting it tothefaction of said` teeth a suicient number of times to effect a,

change in at least one of the properties of adhesive requirement, oil. absorption and ,gloss-im- `partingquality of said calcium sulphite of .notless-than one-tenth of the originalvalue of saidproperty.

11. The method 0f modifying calcium sulphite :I

`which comprises directing -said calciumv sulphite in association with water, linto the path of. travel of hammers of a rotor element, subjecting said calcium. sulphite to percussions from said hammers, said hammers having. a velocity ofnot less thanlol) feet-per second at the pointsof said perg cussionscsaid rotor element at the time of sub-l jecting said calcium sulphite to the action of said hammers being free from contact with said calf,

cium sulphite except :in respect to said hammers,

said." calcium 'sulphite'.,being' free` for movement upon, and at vthe points of, said percussions, said ,calcium sulphite being propelled bysaid hammers away fromfandi'out of the path of travel of said hammers, redirecting the "thus treated calcium sulphite into the Apath of travel of said hammers, andresubjecting it tothe action of said hammers alsufcientunumber of :times to-eiect a change in at least one of the propertiesof adhesive requirement, oil absorption and yglossimparting quality 10.0 feet. per second at` the points of said percussionsisaid circular saw ati-the time of subjecting said slurry to theaction of'said teeth beingfree from contact with saidI slurry; except Ainrespect to said teeth; said slurry being-.free for movementupon, and at thepoints of, said percussionsysaid slurryibeingpropelled by said1teeth -aWay from andout -ofvthepath of travel :of said teeth, redifrecting the `thustreatedslurry into the.l path oi` 13. The method of modifying calcium sulphite which comprises directing said calcium sulphite in association with Water, in the form of a slurry, said slurry constituting atleast one jet, into the path of travel of percussive members of a rotor element, subjecting said slurry to percussions 4from said percussive members, said `percussive members having a velocity of not less than 100 feet per second at the points of said percussions, said rotor element at the time of subjecting said slurry to the action of said percussive members being free from contact with said slurry except in respect to said percussive members, said slurry being free for movement upon, and at the points of, said percussions, said slurry being propelled by said percussive members away from and out of the path of travel of said percussive members, redirecting the thus treated slurry, constituting at least one jet, into the path of travel of said percussive members, and resubjecting it to the action of said percussive members a. sufiicient number -oftimes to effect a change in at least one of the properties of adhesive requirement, oil absorption and gloss-imparting quality of said calcium sulphite of not less than one-tenth of the original value of said property.

14. The method of modifying calcium sulphite which comprises directing said calcium sulphite in association with water, in the form ofa slurry, said slurry constituting at least one jet, into the 14 path of travel of teeth of a circular saw, subjecting said slurry to percussions from said teeth, said teeth having a velocity of not less than 300 feet per second at the points of said percussions, said circular saw at the time `of subjecting said slurry to the action of said teeth being free from contact with said slurry except in respect to said teeth, said slurry being free for movement upon, and at the points of, said percussions, said slurry being propelled by said teeth away from and out of the path of travel of said teeth, redirecting the thus treated slurry, constituting at least one jet, into the path of travel of said teeth, and resub` jecting it to the action of said teeth a sucient number of times to effect a change in at least one of the properties of adhesive requirement, oil absorption and gloss-imparting quality 4of said cal-` cium suiphite` of not less than one-tenth of the original value of said property.

HAROLD R. RAFTON.

REFERENCES CITED The following references `are of record in the Turbett July 6, 1943 

